CN111971334A - Composite of non-polar organic polymer and ultra-low wettability carbon black - Google Patents

Abstract

A semiconductive composite consisting essentially of a non-polar organic polymer and an electrically conductive effective amount of ultra-low wettability carbon black. Further, a method of manufacturing the composite material; a cross-linked polyethylene product made by curing the composite material; an article comprising the composite or product of the invention in shaped form; and methods of using the composites, products or articles of the invention.

Description

Composite of non-polar organic polymer and ultra-low wettability carbon black

Technical Field

Composites of organic polymers and carbon black and related aspects.

Introduction to the word

Patents in the field include US 6,277,303B 1; US 6,284,832B 1; US 6,331,586B 1; and US 7,767,910B 2. US 6,277,303B1 and US 6,284,832B1 examples use Vulcan XC 72 carbon black. The US 6,331,586B1 example uses one of the following: printex XE2 carbon Black (Degussa), Black Pearls 1000 carbon Black (Cabot Corp.), Vulcan XC 72 carbon Black (Cabot Corp.), Ketjenblack EC600JD carbon Black (Akzo), Vulcan P carbon Black (Cabot), United 120 carbon Black (Cabot) or Denka Black carbon Black (Denka). US 7,767,910B2 examples use Vulcan XC 500 carbon black. Cabot corp. Cabot Corporation of birerica, ma (Cabot Corporation, Billerica, Massachusetts, USA). Another carbon black is acetylene black AB 100% -01 (Soltex, Inc., Houston, Texas, USA). Each of the foregoing carbon blacks does not have the ultra-low wettability characteristics.

Disclosure of Invention

We believe that the high content of carbon black in existing semiconductive composites used in the semiconductive layers of medium to extra high voltage power cables may cause undesirable problems. These problems include undesirably high moisture absorption in the semiconductive layers during operational use of the power cable. It is also believed that too low a content of carbon black in these semiconductive composites may lead to other undesirable problems in the power cable, such as too high a volume resistivity or lack of electrical percolation (electrical percolation). One challenge is to reduce the carbon black content in the semiconductor composite without destroying the desired electrical properties of the material.

Prior attempts to solve these problems have combined partially immiscible polar and non-polar polymers with existing carbon blacks to form semiconductive composites having at least one continuous polymeric phase. Some of the existing carbon blacks are located in one of the continuous phases or at the interface between the two phases, and some of the carbon blacks are located in the discontinuous phase. The results are generally unsatisfactory because the carbon black is only partially isolated and/or the carbon black is poorly dispersed in its major separate phase. We provide here an alternative simplified technical solution that overcomes the negative effects of too high and too low carbon black content without resorting to the use of immiscible polar and non-polar polymers. Embodiments of the technical solution include those described below.

A semiconductor composite consisting essentially of: a non-polar organic polymer and a conductive effective amount of ultra-low wettability carbon black.

A method of manufacturing a semiconductor composite material.

An electrical conductor device comprising a conductor core and a semiconductor layer disposed thereon, the semiconductor layer comprising a semiconductor composite.

A method of transmitting electricity through a conductor core of an electrical conductor device.

Detailed Description

The summary and abstract are incorporated herein by reference.

The ultra-low wettability of the ultra-low wettability carbon black can be characterized by any suitable technique or method. Examples are Oil Absorption Number (OAN), moisture absorption number and surface wettability profile, all of which are described later.

The non-polar organic polymer is structurally different from the polar organic polymer omitted and excluded by the semiconductor composite. The non-polar organic polymer may be any homopolymer made by polymerizing an unsubstituted olefin monomer containing 1 or 2 carbon-carbon double bonds, or any copolymer made by polymerizing two or more different unsubstituted olefin monomers independently containing 1 or 2 carbon-carbon double bonds. Each of the olefin monomers may independently be acyclic or cyclic. The acyclic olefin monomer can be linear or branched, and the linear olefin monomer can be an alpha-olefin or a linear diene. The non-polar organic polymer may be free of silicon atoms or may contain copolymerized olefin-functional hydrolyzable silane comonomers therein or grafted thereon.

In some aspects, the non-polar organic polymer can be a non-polar vinyl polymer. The non-polar vinyl polymer consists essentially of: from 50 weight percent (wt%) to 100 wt% derived from ethylene (H)₂C＝CH₂) And from 50 wt% to 0 wt% of constituent units derived from at least one unsubstituted olefin comonomer and/or olefin-functional hydrolyzable silane comonomer, respectively, other than ethylene. The olefin comonomer may be unsubstituted (C)₃-C₂₀) Olefins, or unsubstituted (C)₄-C₂₀) Olefins, or unsubstituted (C)₄-C₈) An olefin, or 1-butene, or 1-hexene, or 1-octene. The non-polar vinyl polymer may be a polyethylene homopolymer or an ethylene/alpha-olefin copolymer. The non-polar vinyl polymer may be free of silicon atoms or may contain copolymerized olefin-functional hydrolyzable silane comonomers therein or grafted thereon. The non-polar propylene-based polymer may consist essentially of: from 50 to 100% by weight of a catalyst derived from propylene (H)₂C＝CHCH₃) And 50 to 0 wt% of constituent units derived from an olefin comonomer which is a hydrocarbon selected from the group consisting of: ethylene, (C)₄-C₂₀) Alpha-olefins, (C)₄-C₂₀) Dienes and combinations of any two or more thereof.

Certain embodiments of the invention are described below as numbered aspects for ease of cross-referencing.

Aspect 1. a semiconductor deviceA composite consisting essentially of: (A) non-polar polyolefin polymers (e.g., non-polar ethylene-based or propylene-based polymers); and a conductively effective amount of (B) ultra-low wettability carbon black (ULW-CB) having a BET nitrogen surface area of 35 to 190 square meters per gram (m) as measured by the Brunauer-Emmett-Teller, BET nitrogen surface area test method (described later)²(iv)/g); and an Oil Absorption Number (OAN) of 115 to 180 milliliters of oil per 100 grams (mL/100g) (115 to 180 cubic centimeters per 100 grams (cc/100g)) as measured by an oil absorption number test (described later). (A) Non-polar polyolefin polymers (e.g., non-polar ethylene-based or propylene-based polymers) may be characterized by: the polar component of the surface energy is greater than 0 to less than or equal to 5 millijoules per square meter (mJ/m) as measured by the surface energy test method described later²). (A) The non-polar polyolefin polymer (e.g., a non-polar ethylene-based or propylene-based polymer) can be a polymer having a monomodal molecular weight distribution (MWD, M)_w/M_n) Such as single Low Density Polyethylene (LDPE), Medium Density Polyethylene (MDPE) or High Density Polyethylene (HDPE). Alternatively, (a) the non-polar polyolefin polymer (e.g., a non-polar ethylene-based or propylene-based polymer) may be of multimodal MWD (M)_w/M_n) Multicomponent polymers of polymers, for example in bimodal LDPE. (A) The multimodal MWD polymer embodiments of (a) can be made in a single reactor using two different catalysts (e.g., a Ziegler-Natta catalyst and a metallocene catalyst or two different metallocene catalysts) or the same catalyst under two different reactor conditions, or in two different reactors, or can be made by blending two different unimodal MWD polymers together, e.g., blending a unimodal MWD LDPE and a unimodal MWD Linear Low Density Polyethylene (LLDPE).

Aspect 2. the semiconductor composite according to aspect 1, wherein (B) ULW-CB is characterized by any one of the restrictions (i) to (iii): (i) the BET nitrogen surface area of (B) ULW-CB, as measured by the BET nitrogen surface area test method, is from 40 to 63m²(ii)/g; and an OAN of 120 to 150mL/100g as measured by the oil absorption number test method; (ii) by BET nitrogen surface area test methodMeasurement of BET nitrogen surface area of (B) ULW-CB of 120 to 180m²(ii)/g; and an OAN of 150 to 175mL/100g as measured by the oil absorption number test method; and (iii) (B) ULW-CB is a ULW-CB blend having (i) and (ii). (i) An example of (a) is the LITX 50 conductive additive. (ii) An example of (a) is LITX 200 conductive additive. (iii) An example of (a) is a mixture of LITX 50 and LITX 200 conductive additives. The LITX 50 and LITX 200 conductive additives are carbon black products from cabot corporation used in the electrodes of lithium ion batteries. The LITX 50 conductive additive has the following and in some aspects (B) ULW-CB is characterized by the following: BET nitrogen surface area of 45 to 60m as measured by the BET nitrogen surface area test method²(ii)/g; and an OAN of 125 to 145mL/100g as measured by the oil absorption number test method. The LITX 200 conductive additive has the following and in some aspects (B) ULW-CB is characterized by the following: a BET nitrogen surface area of 125 to 175m as measured by the BET nitrogen surface area test method²(ii)/g; and an OAN of 152 to 172mL/100g as measured by the oil absorption number test method.

Aspect 3. a semiconductor composite consisting essentially of: (A) non-polar polyolefin polymers (e.g., non-polar ethylene-based or propylene-based polymers); and a conductively effective amount of (B) an ultra-low wettability carbon black (ULW-CB) having a surface wettability profile characterized by: the wettability at 0.02 surface coverage is 0.0101 or less, and the wettability at 0.04 surface coverage is 0.0101 or less, and the wettability at 0.06 surface coverage is 0.0099 or less, and the wettability at 0.08 surface coverage is 0.0111 or less, and the wettability at 0.10 surface coverage is 0.0113 or less, as measured by reverse gas chromatography (IGC) according to the wettability test method (described later).

Aspect 4. the semiconductor composite according to any one of aspects 1 to 3, wherein (B) ULW-CB is characterized by any one of restrictions (i) to (vii): (i) a BET nitrogen surface area of 40 to 180m as measured by the BET nitrogen surface area test method²G, or 40 to 63m²G, alternatively 150 to 175m²(ii)/g; (ii) the water absorption amount is 400 to 2400 parts per million (ppm, weight) as measured by a moisture absorption amount test method (described later)Amount), alternatively 450 to 1,000ppm, alternatively 501 to 600 ppm; (iii) surface wettability profiles characterized by: wettability at 0.02 surface coverage is ≦ 0.0058, and wettability at 0.04 surface coverage is ≦ 0.0070, and wettability at 0.06 surface coverage is ≦ 0.0075, and wettability at 0.08 surface coverage is ≦ 0.0086, and wettability at 0.10 surface coverage is ≦ 0.0091, measured by IGC according to the wettability test method; alternatively, a surface wettability profile characterized by: a wettability at 0.02 surface coverage of ≦ 0.0014, and at 0.04 surface coverage of ≦ 0.0039, and at 0.06 surface coverage of ≦ 0.0051, and at 0.08 surface coverage of ≦ 0.0061, and at 0.10 surface coverage of ≦ 0.0069, measured by IGC according to the wettability test method; (iv) both (i) and (ii); (v) (ii) both (i) and (iii); (vi) both (ii) and (iii); (vii) (iv) a combination of (i), (ii), and (iii). The LITX 50 and LITX 200 conductive additives independently have the aforementioned surface wettability profiles. In some aspects, (B) ULW-CB is characterized such that the total BET nitrogen surface area of (B) ULW-CB, measured in an amount of 10 wt% in the semiconductor composite, is less than 6.0m, as measured by BET nitrogen surface area test method²(ii) in terms of/g. (B) ULW-CB also has very low moisture absorption relative to existing carbon blacks.

Aspect 5. the semiconductive composite according to any of aspects 1 to 4, which does not contain any carbon black other than the ultra-low wettability carbon black.

Aspect 6 the semiconductor composite material according to any one of aspects 1 to 5, characterized in that any one of (i) to (v): (i) consisting essentially of: 61.0 to 99.0 wt% of (A) a non-polar polyolefin polymer; and 39.0 wt% to 1.0 wt% (B) ULW-CB; the above being the total weight of the semiconductor material; (ii) (a) the non-polar polyolefin polymer is a non-polar vinyl polymer; (iii) both (i) and (ii); (iv) (a) the non-polar polyolefin polymer is a non-polar propylene-based polymer; and (v) both (i) and (iv).

Aspect 7. the semiconductor composite of any one of aspects 1 to 6, further consisting essentially of: at least one additive selected from the group consisting of: (C) a plastomer; (D) an antioxidant; (E) an organic peroxide; (F) a scorch retarder; (G) an alkenyl functional coagent; (H) a nucleating agent; (I) a processing aid; (J) an extender oil; (K) stabilizers (e.g., compounds that inhibit Ultraviolet (UV) light-related degradation). At least one additive is different from components (A) and (B), at least in composition.

Aspect 8 the semiconductor composite according to any one of aspects 1 to 7, characterized by the following: examples thereof with varying amounts of (B) ULW-CB a first series, wherein the log (volume resistivity) profile of the first series is <1.0log (Ohm-centimeter, Ohm-cm) at 33 wt% electrically conductive effective amount and <4.5log (Ohm-cm) at 20 wt% electrically conductive effective amount and <10.0log (Ohm-cm) at 15 wt% electrically conductive effective amount and <16.5log (Ohm-cm) at 10 wt% electrically conductive effective amount and <17.5log (Ohm-cm) at 5 wt% electrically conductive effective amount, as measured by volume resistivity test method (described later), wherein the electrically conductive effective amount of (B) ULW-CB is based on the total weight of the semiconductor composite. In some aspects, the log (volume resistivity) profiles of the first series are 0.61log (Ohm-cm) to 0.90log (Ohm-cm) at 33 wt% electrically conductive effective amount, and 1.3log (Ohm-cm) to 4.4log (Ohm-cm) at 20 wt% electrically conductive effective amount, and 7.5log (Ohm-cm) to 9.9log (Ohm-cm) at 15 wt% electrically conductive effective amount, and 15.1log (Ohm-cm) to 16.4log (Ohm-cm) at 10 wt% electrically conductive effective amount, and 16.1log (Ohm-cm) to 17.4log (Ohm-cm) at 5 wt% electrically conductive effective amount, wherein the electrically conductive effective amount of (B) ULW-CB is based on the total weight of the semiconductor composite.

The semiconductor composite according to any one of claims 1 to 8, characterized by a second series of its embodiments of (B) ULW-CB with different total BET N2 surface areas, wherein the second series has a log (volume resistivity) profile of log (volume resistivity) of 15.0 to 20.0m, measured by volume resistivity test method²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 2Log (Ohm-cm); and is between 10.0 and 15.0m²(ii) a total BET N2 surface area of ≦ 4Log (Ohm-cm) for carbon black in the composite; and is in the range of 7.5 to 10m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 10Log (Ohm-cm); and is between 5.0 and 7.5m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 16Log (Ohm-cm); and is in the range of 2.5 to 5.0m²The carbon black in the composite has a total BET N2 surface area of ≦ 17.1Log (Ohm-cm). In some aspects, the log (volume resistivity) profile of the second series is between 15.0 and 20.0m²(ii) the carbon black in the composite has a total BET N2 surface area of 0.5 to 1.9Log (Ohm-cm); and is between 10.0 and 15.0m²(ii) the carbon black in the composite has a total BET N2 surface area of 1.7 to 3.9Log (Ohm-cm); and is in the range of 7.5 to 10m²(ii) the carbon black in the composite has a total BET N2 surface area of 8.1 to 9.9Log (Ohm-cm); and is between 5.0 and 7.5m²(ii) the carbon black in the composite has a total BET N2 surface area of from 14.0 to 15.9Log (Ohm-cm); and is in the range of 2.5 to 5.0m²The carbon black in the composite has a total BET N2 surface area of 16.5 to 17.1Log (Ohm-cm). In some aspects, the log (volume resistivity) profile of the second series is further characterized by a log (volume resistivity) profile in the range of 20.0 to 30.0m²The carbon black in the composite has a total BET N2 surface area of 0.7Log (Ohm-cm) or 0.3 to 0.6Log (Ohm-cm). The first series (or set) of embodiments of aspect 8 may be the same as or different from the second series (or set) of embodiments of aspect 9.

Aspect 10 a method of making the semiconductive composite of any of aspects 1 to 9, the method comprising mixing (B) ultra-low wettability carbon black (ULW-CB) into a melt of (a) a non-polar polyolefin polymer (e.g., a non-polar ethylene-or propylene-based polymer) to obtain the semiconductive composite as a molten blend comprising ingredients (a) and (B). In some aspects, the method further comprises mixing one or more additives (e.g., one or more of ingredients (C) through (K)) into the melt of (a). The method can further comprise extruding the molten blend to obtain an extrudate of the semiconductor composite. In some aspects, the method further comprises allowing the molten blend or extrudate to cool resulting in a solid blend or solid extrudate, respectively.

Aspect 11. a crosslinked polyethylene product which is the product of curing the semiconductive composite according to any one of aspects 1 to 9. In some aspects, the semiconductive composite is cured and further comprises 0.1 wt% to 3 wt% (E) of an organic peroxide and no more than 98.80 wt% or 98.75 wt%, respectively, (a) of a non-polar polyolefin polymer (e.g., a non-polar ethylene-based or propylene-based polymer).

Aspect 12 an article comprising a semiconductive composite according to any one of aspects 1 to 9 or made by the method according to aspect 10, or a crosslinked polyethylene product according to aspect 11, in shaped form. The shaped form of the article may be cylindrical, helical or irregularly shaped. In some aspects, the article can be a semiconductor layer of an electrical conductor device according to aspect 13 (below). In some aspects, the article can be an electrical conductor device according to aspect 13.

Aspect 13. an electrical conductor device comprising a conductive core and a semiconducting layer at least partially covering the conductive core, wherein at least a portion of the semiconducting layer comprises the semiconducting composite according to any of aspects 1 to 9 or made by the method according to aspect 10, or the crosslinked polyethylene product according to aspect 11. When the semiconductive composite is used as a shield (conductor shield or strand shield; insulation shield) and protective jacket in an electrical power transmission/distribution cable (including low, medium, high and extra high voltage), the amount of semiconductive composite in the semiconductive layer of the electrical conductor device can be an amount effective to provide electrical conductivity to dissipate electrical charge. An effective amount may be an amount sufficient for the semiconductor composite to achieve a volume resistivity of less than 100,000Ohm-cm, alternatively from greater than 0Ohm-cm to less than 100,000Ohm-cm, alternatively from >0Ohm-cm to less than 50,000 Ohm-cm. The semiconductor layer may be composed of a single layer, at least a portion of which is the composite or product of the present invention; or consist of multiple layers, at least one of which comprises the composite material or product of the invention. The electrical conductor means may be a coated wire or a power cable. The electrical conductor device may be used in power transmission/distribution applications, including low, medium, high and extra high voltage applications.

Aspect 14 a method of conducting electricity, the method comprising applying a voltage across a conductive core of an electrical conductor device according to aspect 13 so as to generate a current through the conductive core. The applied voltage may be low (>0 kilovolts (kV) to <5kV), medium (5kV to <69kV), high (69kV to 230kV) or extra high (>230 kV).

Aspect 15 a thermally cycled semiconductor composite made by subjecting the semiconductor composite of any one of aspects 1 to 9 to thermal cycling comprising heating the semiconductor composite to 170 ℃ to 190 ℃ for 1 minute to 5 minutes and then cooling to 30 ℃ resulting in a cooled thermally cycled semiconductor composite. Optionally, the heating step can be repeated 1 or more times on the cooled thermally cycled semiconductor composite. Examples of thermal cycling are described later in the thermal cycling test method.

The non-polar polyolefin polymer according to any of the preceding aspects may be a non-polar ethylene-based polymer, or a non-polar propylene-based polymer, or a blend of a non-polar ethylene-based polymer and a non-polar propylene-based polymer.

In the case of a semiconductor composite, "consisting essentially of … …" means that the semiconductor composite contains less than 5.0 wt%, or less than 1.0 wt%, or is free of (i.e., does not contain any added or detectable amount, such as 0.0 wt%) polar organic polymer. The polar organic polymer may be a polar organic homopolymer (e.g., polyester or polyamide) or a polar organic copolymer (e.g., ethylene/unsaturated carboxylic acid ester copolymer). For example, the semiconductive composite is free of polar vinyl copolymers, such as vinyl copolymers made from ethylene and a comonomer that is an unsaturated carboxylic acid or ester. In some aspects, the semiconductor composite is further free of polar organic polymers or copolymers, wherein at least one of the monomers and any one or more comonomers contains one halogen atom (e.g., F, Cl, Br, or I) and/or a carbon-bonded heteroatom group such as (alcohol-based) C-O, (epoxy or ether-based) C-O-C, (aldehyde or ketone-based) C ═ O, (carboxylic acid group) C (═ O) -O, (carboxamide group) C (═ O) -N, (urea-based) N-C (═ O) -N, (amino) C-N, (imino or oxime-based) C ═ N, (amidine) C (═ N) -N, (guanidine-based) N-C (═ N) -N, (nitrile-based) C ≡ N, (thiocarbamate or ester-based) C (═ O) -S, C ≡ N, (thiocarbamate or ester-based) C ═ O) -S, C ≡ N, and C ≡ O-N, C-S (of a thiol group), C-S-C (of a thioether group), or a collection of said macromolecules. In some embodiments, the semiconductor composite is also free of poly (arylethylene), such as polystyrene.

"Polymer" means a homopolymer or a copolymer. Homopolymers are macromers composed of monomer units derived from only one monomer and no comonomer. Copolymers are macromers having monomer units and comonomer units, wherein the monomer units are made by polymerizing a first monomer and the comonomer units are made by polymerizing one or more different second monomers or more monomers known as comonomers. The polymer also includes a collection of said macromolecules. The monomers and comonomers are polymerizable molecules. Monomeric units (monomeric units), also referred to as monomeric units (monomeric units) or "mers", are the largest building blocks that a single monomer molecule contributes (derivatizes) to the structure of one or more macromolecula. Comonomer units (comonomeric units), also known as comonomer units (comonomer units) or "interpolymers (comers)," are the largest building blocks that a single comonomer molecule contributes (derives) to the structure of one or more macromolecules. Each unit is typically divalent. A "bipolymer" is a copolymer made from monomers and one comonomer. A "terpolymer" is a copolymer made from a monomer and two different comonomers. Vinyl copolymers are such copolymers in which the monomer units are derived from the monomer ethylene (CH)₂＝CH₂) And comprises on average at least 50 weight percent macromers per molecule, and comonomer units derived from one or more comonomers described herein and comprising on average per molecule>0% by weight to at most 50% by weight of macromers.

The terms "cure" and "crosslinking" are used interchangeably herein to mean the formation of a crosslinked product (network polymer).

By "electrically conductive effective amount" is meant that the amount of ultra-low wettability carbon black in the semiconductive composite is sufficient to exceed its percolation threshold. That is, the amount of ultra-low wettability carbon black is sufficient by itself to enable conduction through the semiconductor composite using ULW-CB. In the semiconductor layer disposed on the electrical conductor, the semiconductor composite having an electrically conductive effective amount should achieve a volume resistivity of less than 100,000 Ohm-cm.

Unless specifically stated otherwise, "log (volume resistivity)" is measured in log (Ohm-cm) on samples that have not been subjected to thermal cycling. It is sometimes written as "log (volume resistivity) (no thermal cycle)". To eliminate all doubt, the log (Ohm-cm) values expressed in terms of number and in the claims are log (volume resistivity) (no thermal cycling) values.

"(meth) acrylate" includes acrylate, methacrylate, and combinations thereof. The (meth) acrylate may be unsubstituted.

"polar organic copolymer": macromers prepared from one monomer and 0,1 or more comonomers, wherein at least one of the monomer and the one or more comonomers contains halogen atoms (e.g., F, Cl, Br, or I) per molecule; and/or carbon-bonded heteroatom groups, such as C — O (of alcohol groups), C — O (of epoxy or ether groups), C ═ O (of aldehyde or ketone groups), C (═ O) -O (of carboxylic or ester groups), C (═ O) -N (of carboxamide groups), N — C (═ O) -N (of urea groups), C — N (of amino groups), C ═ N (of imino or oxime groups), C (═ N) -N (of amidine groups), N — C (═ N) -N (of guanidine groups), C ≡ N (of nitrile groups), C (═ O) -S (of thiocarbamate or ester groups), C — S (of thiol groups), C — S (of thioether groups) or a collection of said macromolecules.

A semiconductor composite material. It consists essentially of: a single nonpolar polymer as component (a); and contains a percolation effective loading of (B) ultra low wettability carbon black (ULW-CB). The composite material may optionally consist essentially of: for example, zero, one or more of the additives (C) to (K). The total weight of the semiconductor composite was 100.00 wt%.

Semiconductor composites can be made in many different ways. In some aspects, the semiconductor composite may be made by: mixing (a) a melt of a non-polar polyolefin polymer (e.g., a non-polar ethylene-based or propylene-based polymer) with (B) ultra-low wettability carbon black (ULW-CB) and any optional ingredients (e.g., any zero, one or more of ingredients (C) through (K)) to obtain a semiconductor composite as a mixture of ingredients (a), (B), and any optional ingredients. Mixing may comprise compounding, kneading or extruding. To facilitate mixing, one or more ingredients (e.g., (B), additives (C), (D), (E), etc.) may be provided in a portion of (a) in the form of an additive masterbatch or in the form of a dispersion in a non-polar carrier resin other than (a). The non-polar carrier resin may be a polypropylene polymer.

Another method by which a semiconductive composite containing one or more optional ingredients, such as additives (C) to (K), can be made is by making the semiconductive composite in an unmelted form, e.g., in pellet form, composed of (a) and (B) ultra-low wettability carbon black (ULW-CB), and contacting the unmelted form with the optional ingredients. Contacting may comprise soaking, dipping or injecting. The contacting may be carried out at a temperature of about 20 ℃ to 100 ℃ for 0.1 hour to 100 hours, for example 60 ℃ to 80 ℃ for 0.1 hour to 24 hours.

The semiconductor composite may be prepared as a one-part formulation, or a multi-part formulation, such as a two-part formulation, or a three-part formulation. The one-part formulation contains all of the ingredients of the semiconductor composite embodiment. A multi-part formulation contains multiple parts with different or certain amounts of the components of the semiconductor composite embodiment in different parts. If desired, different parts of a multi-part formulation may be combined to give a single-part formulation. There is no inherent reason why one or more parts of these formulations cannot include any combination of ingredients.

The semiconductor composite may be in a divided solid form or in a continuous form. The segregated solid form may comprise particles, pellets, powder, or a combination of any two or more thereof. The continuous form may be a molded part (e.g., a blow molded part) or an extruded part (e.g., an insulation layer of an electrical conductor device). The semiconducting composite may be crosslinked by radiation curing or organic peroxide/thermal curing. If desired, the semiconductor composite may be cooled to a storage temperature (e.g., 23 ℃) and stored for a period of 1 hour, 1 week, 1 month, or longer.

The component (a) is a nonpolar polyolefin polymer (for example, a nonpolar vinyl or propylene-based polymer). (A) The non-polar polyolefin polymer may be a single component non-polar ethylene-or propylene-based polymer (having a monomodal molecular weight distribution) or a blend of two or more of said non-polar polyolefin polymers. Each (a) non-polar polyolefin polymer may be a cross-linkable or cross-linked (cured) single or multi-phase (e.g., amorphous and crystalline) material. Copolymers include copolymers, terpolymers, and the like.

(A) The non-polar polyolefin polymer may be a polyethylene homopolymer containing from 99 wt% to 100 wt% of vinyl monomer units. The polyethylene homopolymer may be a High Density Polyethylene (HDPE) homopolymer made by coordination polymerization or a Low Density Polyethylene (LDPE) homopolymer made by free radical polymerization.

Alternatively, (A) the non-polar polyolefin polymer may be a polymer containing from 50 wt% to<100 wt% of vinyl monomer unit and 50 wt% to 0 wt% (C)₃-C₂₀) An ethylene/alpha-olefin copolymer of alpha-olefin derived comonomer units. (A) Examples of the ethylene/α -olefin copolymer of (a) may be Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MDPE), or High Density Polyethylene (HDPE). Alternatively, the polyethylene polymer may be a Low Density Polyethylene (LDPE). The ethylene/alpha-olefin (alpha-olefin/"alpha-olefin") interpolymer has an alpha-olefin content of at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, or at least 25 wt%, based on the weight of the entire interpolymer. The alpha-olefin content of these interpolymers can be less than 50 wt%, less than 45 wt%, less than 40 wt%, or less than 35 wt%, based on the weight of the entire interpolymer. Exemplary ethylene/α -olefin interpolymers are ethylene/propylene, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, ethylene/diene containing from 20 wt% to 1 wt% diene comonomer units, ethylene/propylene/1-octene, ethylene/propylene/1-butene, ethylene/1-butene/1-octene, containing from 50 wt% to 100 wt% ethylene monomer units, from 49 wt% to 1 wt% of diene comonomer units>Ethylene/propylene/diene (EPDM) having from 0% by weight of propylene comonomer units and from 20% to 1% by weight of diene comonomer units. ForThe diene that independently makes diene comonomer units in the ethylene/diene copolymer or in the EPDM can be 1, 3-butadiene, 1, 5-hexadiene, 1, 7-octadiene, ethylidene norbornene, dicyclopentadiene, vinyl norbornene, or a combination of any two or more thereof.

(A) (C) in the case of an ethylene/alpha-olefin copolymer of a nonpolar polyolefin polymer (e.g., a nonpolar vinyl or propylene-based polymer)₃-C₂₀) The alpha-olefin may be a compound of formula (I): h₂C ═ C (h) -R (i), wherein R is linear (C)₁-C₁₈) An alkyl group. (C)₁-C₁₈) Alkyl is a monovalent unsubstituted alkene having 1 to 18 carbon atoms. Examples of R groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. In some embodiments, (C)₃-C₂₀) The alpha-olefin is 1-propylene, 1-butene, 1-hexene or 1-octene; or 1-butene, 1-hexene or 1-octene; or 1-butene or 1-hexene; or 1-butene or 1-octene; or 1-hexene or 1-octene; or 1-butene; or 1-hexene; or 1-octene; or a combination of any two of 1-butene, 1-hexene and 1-octene. Alternatively, the α -olefin may have a cyclic structure, such as cyclohexane or cyclopentane, yielding an α -olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane. (C)₃-C₂₀) Alpha-olefins may be used as comonomers with ethylene monomers.

Alternatively, (a) the non-polar polyolefin polymer may be an ethylene/olefin functional silane copolymer. The olefin-functional silane comonomer used to make the ethylene/olefin-functional silane copolymer may be a hydrolysable silane monomer of paragraph [0019] of Chaudhary's WO 2016/200600A1 (PCT/US 16/033879 filed 5/24/2016) or of U.S. Pat. No. 5,266,627 to Meverden et al. Olefin-functional hydrolyzable silanes can be grafted (post-reactor) onto the copolymer embodiment of (A). Alternatively, the olefin-functional hydrolyzable silane may be copolymerized with ethylene and a comonomer to directly make the hydrolyzable silane group containing copolymer embodiment. In some aspects, the alkene-functional hydrolyzable silane is Vinyltrimethoxysilane (VTMS), Vinyltriethoxysilane (VTES), vinyltriacetoxysilane, or gamma- (meth) acryloxypropyltrimethoxysilane, and the hydrolyzable silane group is 2-trimethoxysilylethyl, 2-triethoxysilylethyl, 2-triacetoxysilylethyl, or 3-trimethoxysilylpropoxycarbonylethyl or 3-trimethoxysilylpropoxycarbonylpropyl.

(A) The non-polar polyolefin polymer can be a blend of two or more different (a) non-polar polyolefin polymers (e.g., non-polar ethylene-based and/or propylene-based polymers) or the reaction product of a polymerization reaction conducted with two or more different catalysts. (A) The non-polar polyolefin polymer may be made in two or more reactors, for example a non-polar vinyl polymer, ELITE from The Dow Chemical Company^TMA polymer.

(A) The non-polar polyolefin polymer (e.g., a non-polar ethylene-based or propylene-based polymer) can be made by any suitable method, many of which are known. Any conventional or hereafter discovered method for producing polyethylene polymers may be used to prepare (a). Typically, the production process comprises one or more polymerization reactions. For example, LDPE can be prepared using a high pressure polymerization process. Alternatively, LDPE may be produced using a coordination polymerization process using one or more polymerization catalysts such as Ziegler-Natta, chromium oxide, metallocene, post-metallocene catalysts. Suitable temperatures are from 0 ℃ to 250 ℃ or 30 ℃ or 200 ℃. Suitable pressures are from atmospheric (101kPa) to 10,000 atmospheres (about 1,013 megapascals ("MPa")). In most polymerizations, a catalyst to polymerizable olefin (monomer/comonomer) molar ratio of 10 is employed^-121 to 10^-11, or 10^-91 to 10^-5:1。

(A) The amount of non-polar polyolefin polymer (e.g., non-polar ethylene-based or propylene-based polymer) can be 70 wt% to 98.9 wt%, or 80 wt% to 95 wt%, or 80 wt% to 98 wt% of the total weight of the semiconductive composite.

The semiconducting composite is free of (in the absence of added) polar organic polymers, such as polar vinyl polymers, e.g., ethylene/unsaturated carboxylic acid ester copolymers comprising vinyl monomer units and unsaturated carboxylic acid ester (or carboxylic acid) comonomer units. The proportion of unsaturated carboxylic acid ester comonomer units in the polar vinyl copolymer (AA) can be from 5 wt% to 40 wt%, alternatively from 20 wt% to 35 wt%, alternatively from 25 wt% to 31 wt%, based on the weight of (AA). The vinylic units can be from 95 wt% to 60 wt%, alternatively from 80 wt% to 65 wt%, alternatively from 75 wt% to 69 wt%, based on the weight of (AA). Each unsaturated carboxylic acid ester comonomer can independently have a hydrogen atom and from 3 to 20 carbon atoms per molecule, i.e., (C)₃-C₂₀) An unsaturated carboxylic acid ester comonomer.

The unsaturated carboxylic acid ester comonomer from which the omitted and excluded unsaturated carboxylic acid ester comonomer unit is derived may be a vinyl (C)₂-C₈) The carboxylic acid ester, and the ethylene/unsaturated carboxylic acid ester copolymer is ethylene-vinyl (C)₂-C₈) A carboxylate copolymer. In some aspects, vinyl (C)₂-C₈) The carboxylic acid ester is a vinyl ester of a carboxylic acid anion having 2 to 8 carbon atoms, or 2 to 4 carbon atoms. US 7,767,910B2 column 2 lines 34 to 50 mentions examples of vinyl formate. Vinyl radical (C)₂-C₈) The carboxylic acid ester may be vinyl (C)₂-C₄) Carboxylic acid esters, such as vinyl acetate, vinyl propionate, or vinyl butyrate, and the ethylene/unsaturated carboxylic acid ester copolymer may be ethylene-vinyl (C)₂-C₄) A carboxylate bipolymer, or an ethylene-vinyl acetate (EVA) bipolymer, or an ethylene-vinyl propionate bipolymer, or an ethylene-vinyl butyrate bipolymer. EVA copolymers consist essentially of ethylene-derived monomer units and vinyl acetate-derived comonomer units. The EVA dipolymer can have a vinyl acetate comonomer unit content of 5 wt% to 40 wt%, alternatively 20 wt% to 35 wt%, alternatively 25 wt% to 31 wt%, based on the weight of the EVA dipolymer. The wt% values are the average per EVA molecule.Alternatively or additionally, the melt index (190 ℃, 2.16kg) of (a) (e.g., EVA dipolymer) can be 2 grams/10 minutes to 60 grams/10 minutes, or 5 grams/10 minutes to 40 grams/10 minutes, as measured by ASTM D1238-04.

The unsaturated carboxylic acid ester comonomer from which the omitted and excluded unsaturated carboxylic acid ester comonomer unit is derived may also be an alkyl (meth) acrylate, such as (C) (meth) acrylic acid₁-C₈) Alkyl esters, such as methyl acrylate and methyl methacrylate. (meth) acrylic acid (C)₁-C₈) Alkyl esters can be used, for example, in ethylene- (meth) acrylic acid (C)₁-C₈) Are found in the ethylene/unsaturated carboxylic acid ester copolymers of the alkyl ester copolymers (EAA) which are omitted and excluded. In some aspects, (C)₁-C₈) The alkyl group may be (C)₁-C₄) Alkyl, (C)₅-C₈) Alkyl or (C)₂-C₄) An alkyl group. EAA is essentially composed of monomeric units derived from ethylene and one or more different types of (meth) acrylic acid (C)₁-C₈) Alkyl ester derived comonomer units (e.g. ethyl acrylate and/or ethyl methacrylate comonomer units). (C)₁-C₈) The alkyl group may be methyl, ethyl, 1-dimethylethyl, butyl or 2-ethylhexyl. The (meth) acrylate may be an acrylate, a methacrylate, or a combination thereof. (meth) acrylic acid (C)₁-C₈) The alkyl ester may be ethyl acrylate and the EAA may be ethylene-ethyl acrylate copolymer (EEA), or (meth) acrylic acid (C)₁-C₈) The alkyl ester may be ethyl methacrylate and the EAA may be ethylene-ethyl methacrylate copolymer (EEMA). The ethyl acrylate or ethyl methacrylate comonomer units content of the EEA or EEMA may independently be from 5 wt% to 40 wt%, or from 20 wt% to 35 wt%, or from 25 wt% to 31 wt%, respectively, based on the weight of the EEA or EEMA bipolymer.

Component (B): ultra-low wettability carbon black (ULW-CB). ULW-CB is as previously described. (B) The ULW-CB can be 1.0 wt% to 39 wt%, or 1.5 wt% to 29 wt%, or 1.5 wt% to 20.5 wt%, or 1.5 wt% to 19 wt%, or 1.5 wt% to 16 wt%, or 1.5 wt% to 11 wt%, or 1.5 wt% to 6 wt% of the semiconductor composite.

In some aspects, the semiconductive composite may also contain carbon black in addition to (B) ULW-CB. Examples of such further carbon blacks are Printex XE2 carbon Black (degussa), Black Pearls 1000 carbon Black (cabot corporation), Vulcan XC 72 carbon Black (cabot corporation), Ketjenblack EC600JD carbon Black (aksonnobel), Vulcan P carbon Black (cabot corporation), United 120 carbon Black (cabot corporation), Denka Black carbon Black (electric corporation), Vulcan XC 500 carbon Black or acetylene Black AB 100% -01 carbon Black (Soltex). In other aspects, (B) ULW-CB does not include any other carbon black.

Component (C): a plastic body. (C) A plastomer may be a polymeric material combining the qualities of, for example, rubber-like elastomers and plastics with the processing capabilities of the plastics. In some aspects, (C) plastomers may also be embodiments of (a) non-polar polyolefin polymers. (C) Examples of (B) are ethylene/alpha-olefin copolymers having a density of 0.905g/cm³And melt index (I)₂) (ASTM D1238-04, 190 ℃, 2.16kg) 0.9 g/10min of Linear Low Density Polyethylene (LLDPE) available as DFNA-1477NT from the Dow chemical company. In some aspects, the semiconductive composite and the crosslinked polyethylene product are free of (C). When present, (C) may be 0.01 wt% to 1.5 wt%, or 0.05 wt% to 1.2 wt%, or 0.1 wt% to 1.0 wt% of the semiconductor composite.

Optionally ingredient (D) an antioxidant. (D) Antioxidants function to provide antioxidant properties to the semiconductive composite and/or peroxide cured semiconductive product. Examples of suitable (D) are bis (4- (1-methyl-1-phenylethyl) phenyl) amine (e.g., NAUGARD 445); 2,2' -methylene-bis (4-methyl-6-tert-butylphenol) (e.g., VANOX MBPC); 2,2' -thiobis (2-tert-butyl-5-methylphenol) (CAS number 90-66-4, commercial LOWINOX TBM-6); 2,2' -thiobis (6-tert-butyl-4-methylphenol) (CAS number 90-66-4, commercial LOWINOX TBP-6); tris [ (4-tert-butyl-3-hydroxy-2, 6-dimethylphenyl) methyl ] -1,3, 5-triazine-2, 4, 6-trione (e.g., CYANOX 1790); pentaerythritol tetrakis (3- (3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl) propionate (e.g., IRGANOX 1010, CAS number 6683-19-8), 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionic acid 2,2' -thiodiethanediyl ester (e.g., IRGANOX 1035, CAS number 41484-35-9), and distearyl thiodipropionate ("DSTDP"). in some aspects, (D) is bis (4- (1-methyl-1-phenylethyl) phenyl) amine (e.g., NAUGARD 445, available from adivant (Danbury, Connecticut, u.s.a.) in the united states, in some aspects, the semiconductor composite and crosslinked polyethylene product are free of (D) when present, (D) may be 0.01 wt% to 1.5 wt%, or 0.05 wt% to 1.2 wt%, or 0.1 wt% to 1.0 wt% of the semiconductor composite.

Optional ingredient (E): an organic peroxide. A molecule containing carbon atoms, hydrogen atoms and two or more oxygen atoms and having at least one-O-group, with the proviso that when more than one-O-group is present, each-O-group is indirectly bonded to another-O-group through one or more carbon atoms; or a collection of said molecules. If it is desired to cure the semiconductor composite, (E) an organic peroxide may be added to the semiconductor composite, the curing comprising, inter alia, heating the semiconductor composite comprising components (A), (B) and (E) to or above the decomposition temperature of the (E) organic peroxide. (E) The organic peroxide may be of the formula R^O-O-O-R^OMonoperoxides of which each R is^OIndependently is (C)₁-C₂₀) Alkyl or (C)₆-C₂₀) And (4) an aryl group. Each (C)₁-C₂₀) Alkyl is independently unsubstituted or substituted by 1 or 2 (C)₆-C₁₂) Aryl substitution. Each (C)₆-C₂₀) Aryl being unsubstituted or substituted by 1 to 4 (C)₁-C₁₀) Alkyl substitution. Alternatively, (E) may be of the formula R^O-O-O-R-O-O-R^ODiperoxides in which R is a divalent hydrocarbon radical, e.g. (C)₂-C₁₀) Alkylene, (C)₃-C₁₀) Cycloalkylene or phenylene, and each R^OAs defined above. (E) The organic peroxide may be bis (1, 1-dimethylethyl) peroxide; bis (1, 1-dimethylpropyl) peroxide; 2, 5-dimethyl-2, 5-bis (1, 1-dimethylethylperoxy) hexane; 2, 5-dimethyl-2, 5-bis (1, 1-dimethylethyl)Peroxy) hexyne; 4, 4-bis (1, 1-dimethylethylperoxy) pentanoic acid; butyl ester; 1, 1-bis (1, 1-dimethylethylperoxy) -3,3, 5-trimethylcyclohexane; benzoyl peroxide; tert-butyl peroxybenzoate; di-tert-amyl peroxide ("DTAP"); bis (α -tert-butyl-peroxy isopropyl) benzene ("BIPB"); isopropyl cumyl tert-butyl peroxide; t-butyl cumyl peroxide; di-tert-butyl peroxide; 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane; 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexyne-3, 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane; isopropyl cumyl hydroperoxide; 4, 4-di (tert-butylperoxy) pentanoic acid butyl ester; or di (isopropylcumyl) peroxide; or diisopropylphenyl peroxide. (E) The organic peroxide may be dicumyl peroxide. In some aspects, only a blend of two or more (E) organic peroxides is used, for example a 20:80(wt/wt) blend of t-butylcumyl peroxide and bis (t-butylperoxyisopropyl) benzene (e.g., LUPEROX D446B, commercially available from Arkema). In some aspects, at least one, or each (E) organic peroxide contains one-O-group. In some aspects, the semiconductive composite and crosslinked polyethylene product are free of (E). When present, (E) the organic peroxide can be 0.05 wt% to 3.0 wt%, alternatively 0.1 wt% to 3 wt%, alternatively 0.5 wt% to 2.5 wt% of the semiconducting composite. Typically, when the semiconducting composite further comprises (D) an antioxidant and (E) an organic peroxide, the weight/weight ratio of (D) antioxidant to (E) organic peroxide is less than 2((D)/(E) (wt/wt)<2)。

Optionally, component (F) a scorch retarder. A molecule or collection of molecules that inhibits premature curing. Examples of scorch retarders are hindered phenols; a semi-hindered phenol; TEMPO; a TEMPO derivative; 1, 1-diphenylethylene; 2, 4-diphenyl-4-methyl-1-pentene (also known as alpha-methylstyrene dimer or AMSD); and allyl-containing compounds described in US 6277925B1 column 2, line 62 to column 3, line 46. In some aspects, the semiconductive composite and the crosslinked polyethylene product are free of (K). When present, the (K) scorch retarder can be 0.01 wt% to 1.5 wt%, alternatively 0.05 wt% to 1.2 wt%, alternatively 0.1 wt% to 1.0 wt% of the semiconductor composite.

Optionally ingredient (G) an alkenyl functional coagent. A molecule containing the main structure or ring substructure and one, or two or more, propenyl, acrylate and/or vinyl groups bonded to it, where the substructure consists of carbon atoms and optionally nitrogen atoms; or a collection of said molecules. (D) Conventional adjuvants may be free of silicon atoms. When (G) the alkenyl functional coagent may be a propenyl functional conventional coagent as described by limiting any of (i) to (v): (i) (G) is 2-allylphenylallyl ether; 4-isopropenyl-2, 6-dimethylphenylallyl ether; 2, 6-dimethyl-4-allylphenylallyl ether; 2-methoxy-4-allylphenylallyl ether; 2,2' -diallylbisphenol a; o, O' -diallylbisphenol a; or tetramethyldiallylbisphenol A; (ii) (G) is 2, 4-diphenyl-4-methyl-1-pentene or 1, 3-diisopropenylbenzene; (iii) (G) is triallyl isocyanurate ("TAIC"); triallyl cyanurate ("TAC"); triallyl trimellitate ("TATM"); n, N, N ', N', N ", N" -hexaallyl-1, 3, 5-triazine-2, 4, 6-triamine ("HATATA"; also known as N²,N²,N⁴,N4,N⁶,N⁶Hexaallyl-1, 3, 5-triazine-2, 4, 6-triamine); triallyl orthoformate; pentaerythritol triallyl ether; triallyl citrate; or triallyl aconitate; (iv) (G) is a mixture of any two of the propenyl functional auxiliaries in (i). Alternatively, (G) may be an acrylate functional conventional coagent selected from: trimethylolpropane triacrylate ("TMPTA"), trimethylolpropane trimethacrylate ("TMPTMA"), ethoxylated bisphenol a dimethacrylate, 1, 6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and propoxylated glyceryl triacrylate. Alternatively, (G) may be a vinyl functional conventional coagent selected from: polybutadiene having a1, 2-vinyl content of at least 50 wt%, and trivinylcyclohexane ("TVCH"). Alternatively, (G) may be a conventional adjuvant as described in US 5,346,961 or US 4,018,852. Alternatively, (G) may be a combination of the foregoing adjuvants or anyTwo or more. In some aspects, the semiconductive composite and crosslinked polyethylene product are free of (G). When present, the (G) adjuvant may be 0.01 wt% to 4.5 wt%, or 0.05 wt% to 2 wt%, or 0.1 wt% to 1 wt%, or 0.2 wt% to 0.5 wt% of the semiconductor composite.

Optionally ingredient (H) a nucleating agent. Organic or inorganic additives that enhance the crystallization rate of polyethylene polymers. (H) Examples of (B) are calcium carbonate, titanium dioxide, barium sulfate, ultra-high molecular weight polyethylene, potassium hydrogen phthalate, benzoic acid compounds, sodium benzoate compounds, disodium bicyclo [2.2.1] heptane-2, 3-dicarboxylate, zinc monoglycerol oleate and 1, 2-cyclohexanedicarboxylic acid, the calcium salt being zinc stearate. In some aspects, the semiconductive composite and crosslinked polyethylene product are free of (H). When present, the concentration of (H) may be 0.01 wt% to 1.5 wt%, or 0.05 wt% to 1.2 wt%, or 0.1 wt% to 1.0 wt% of the semiconductor composite.

Optionally, ingredient (I) a processing aid. (I) Examples of (b) are fluoroelastomers and Viton FreeFlow processing aids such as Viton FreeFlow 23 from The Chemours Company, Wilmington, Delaware, USA of Wilmington, Delaware, USA, Wilmington. In some embodiments, the semiconductor composite further comprises a masterbatch comprising (C), (D), and (I).

Optionally ingredient (J) an extender oil. (J) Examples of (d) are mineral oil, paraffin oil, and combinations thereof.

Optionally ingredient (K) a stabilizer. A particulate solid having an average particle size of 18 nanometers (nm) to 22 nm. (K) There may be hydrophobated fumed silicas such as those commercially available from cabot corporation under the CAB-O-SIL trade name. (K) May be a UV stabilizer which may also have a flame retardant effect.

The semiconductor composite may independently consist essentially of, or may further consist of from 0.005 wt% to 0.5 wt% of each of one or more optional additives selected from the group consisting of: carrier resin, corrosion inhibitor (e.g. SnSO)₄) Lubricant, anti-blocking agent, antistatic agent, slipping agent, plasticizer, tackifier and surface activityAn agent, an acid scavenger, a voltage stabilizer and a metal deactivator.

Optional additives may be used to impart one or more beneficial properties to the semiconductor composite of the invention and/or the product of the invention. In some aspects, any of the optional ingredients or additives are the ingredients or additives used in the examples hereafter.

An electric conductor device: such as coated metal wires, cables or power cables for low, medium, high and extra-high voltage power transmission applications. "wire" means a single strand or filament of conductive material, such as a conductive metal, e.g., copper or aluminum, or a single strand or fiber optic filament. A "power cable" comprises at least one conductor disposed within a semiconducting layer and a covering, which may be referred to as an insulating layer. The electrical conductor device may be designed and constructed for medium, high or extra-high voltage applications. Examples of suitable cable designs are shown in US 5,246,783; US 6,496,629; and US 6,714,707.

The electrical conductor means may comprise, from the inside to the outside, a conductive core, an inner semiconductive layer and optionally an inner insulating layer. Optional insulating aspects of the electrical conductor device may contain an outer semiconductive layer and an outer insulating layer. The conductive core may be formed from one or more wires. When the conductive core is "stranded," it contains two or more wires that can be subdivided into discrete strands. Each wire in the conductive core, whether bundled or not, may be individually coated with an insulating layer and/or the discrete bundles may be coated with an insulating layer. Each insulating layer may independently be a single or multi-layer cover, coating or jacket. The one or more insulating layers primarily serve to protect or insulate the conductive core and the one or more semiconductive layers from the external environment, e.g., sunlight, water, heat, oxygen, to protect or insulate other conductive materials (e.g., to prevent short circuits), and/or to protect or insulate corrosive substances (e.g., chemical fumes).

The single or multiple layer covering from one insulated electrical conductor means to the next may be arranged differently depending on their respective intended use. For example, seen in cross-section, the multilayer cover of the insulated electrical conductor device may be arranged with the following components in order from its innermost layer to its outermost layer: an inner semiconductive layer (in physical contact with the conductive core), an insulating layer comprising a crosslinked polyethylene product (crosslinked product of the invention), an outer semiconductive layer, a metallic shield, and a protective sheath. The layers and the jacket are circumferentially and coaxially (longitudinally) continuous. The metallic shield (ground shield) is coaxially continuous and circumferentially continuous (one layer) or discontinuous (tape or wire). When present, the outer semiconductive layer may be comprised of a peroxide crosslinked semiconductive product that can be peeled from the insulation layer.

And (3) a conductive method. The method of electrical conduction of the present invention may use an electrical conductor device, or may use a different electrical conductor device comprising the semiconductor composite or product of the present invention.

The electrical conductor device may be used for data transmission applications and/or for power transmission applications, including low, medium, high and extra-high voltage applications.

The semiconductor composites and products of the invention can be used in a variety of other applications, including in containers, vehicle parts, and electronic device packaging.

The compounds include all isotopic and naturally abundant and isotopically enriched forms thereof. The enriched form may have medical or anti-counterfeiting uses.

In some aspects, any compound, composition, formulation, material, mixture, or reaction product herein may be free of any of the chemical elements selected from the group consisting of: H. li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanoids, and actinides; provided that the chemical elements required for the compound, composition, formulation, material, mixture, or reaction product (e.g., C and H for polyethylene or C, H and O for alcohol) are not counted.

Unless otherwise indicated, the following applies. Or, in the alternative, in advance of the different embodiments. AEIC means the Association of Edison illumination Companies, Birmingham, Alabama, USA, of Bermingham, Alabama. ASTM means the Standard organization, American society for testing and materials (ASTM International, West Consho hoken, Pennsylvania, USA), of West Conshohoken. IEC means the Standard organization, International Electrotechnical Commission (International Electrotechnical Commission, Geneva, Switzerland) of Geneva, Switzerland. ISO means the Standard Organization, International Organization for Standardization in Geneva, Switzerland. Any comparative examples are for illustrative purposes only and are not prior art. Absence or absence means complete absence; or not detectable. ICEA means the standard promulgated by the institute of Insulated Cable Engineers (Association) and the IHS Markit of london, england. IUPAC is the International Union of Pure and Applied Chemistry (International Union of Pure and Applied Chemistry) (the IUPAC secretary of Triangle Research Park, N.C.A., USA (IUPAC Secretariat, Research Triangle Park, North Carolina, USA)). Permission selections may be given instead of imperative selections. Operable means functionally capable or effective. Optional (optionally) means absent (or excluded), or present (or included). The properties are measured using standard test methods and conditions for measurement (e.g.viscosity: 23 ℃ C. and 101.3 kPa). Ranges include endpoints, subranges, and all values and/or fractional values contained therein, except for ranges containing integers not including fractional values. Room temperature: 23 ℃ plus or minus 1 ℃. When referring to compounds, substituted means that each substitution has up to and including one or more substituents replacing hydrogen.

The preparation method of the semiconductor composite material comprises the following steps: a semiconductive composite example consisting essentially of 67 wt% (A) of a non-polar polyolefin polymer (e.g., a non-polar vinyl polymer) and 33 wt% (B) of ULW-CB was prepared by: the semiconductive composite examples were obtained as a concentrated masterbatch by melt mixing (a) and (B) using a c.w. brabender premixer at a mixing speed of 50 revolutions per minute (rpm) for 20 minutes at 160 ℃. These melt mixing conditions are well suited when (a) is a non-polar vinyl polymer. The conditions may be adjusted to ensure proper melt mixing of other embodiments of (a), such as the non-polar propylene-based polymer, for example, using higher temperatures (e.g., 200 ℃). If desired, the concentrated masterbatch embodiment of the semiconductive composite is melt mixed with an independently selected (a) nonpolar polyolefin polymer (e.g., nonpolar ethylene-or propylene-based polymer), which may be the same or different from (a) of the concentrated masterbatch, to give (B) an embodiment of the semiconductive composite having a ULW-CB concentration >0 wt% to <33 wt%.

A method for preparing the pellets. The semiconductor composite material produced by the semiconductor composite material production method was compounded into a hopper of a Brabender single-screw extruder, and a melt of the semiconductor composite material was extruded at a screw speed of 25rpm at 120 ℃ to obtain the semiconductor composite material as a molten strand. These extrusion and stranding conditions are well suited when (a) is a non-polar vinyl polymer. Conditions may be adjusted to ensure proper extrusion and stranding of other embodiments of (a), such as non-polar propylene-based polymers, for example, using higher temperatures (e.g., 200 ℃). The molten strands were fed into a Brabender granulator to give a second inventive semiconductive composite in the form of pellets.

A soaking method. 50 grams (g) of the second inventive semiconductive composite pellet prepared in the pellet preparation method and 0.865g (E) of an organic peroxide were added to a 250 milliliter volume of fluorinated high density polyethylene (F-HDPE) bottle. Tightly sealing the bottle containing the pellet and (E). (ii) allowing (E) an organic peroxide to soak into the pellets at 70 ℃ for 8 hours, shaking through a sealed bottle at 0,2, 5, 10, 20 and 30 minutes to obtain a third inventive semiconductor composite as organic peroxide-soaked pellets. The organic peroxide soaked pellets were stored in F-HDPE bottles at 23 ℃ until needed for testing.

Crosslinked polyethylene product and compression molded plaques preparation method 1: compression molded plaques of crosslinked polyethylene products were prepared for dissipation factor testing. 15g of the organic peroxide impregnated pellets prepared by the impregnation method 1 were sandwiched between two 2 millimeter (mm) thick poly (ethylene terephthalate) films to give a sandwich. The sandwich was placed into a mold having the following dimensions: 180 mm. times.190 mm. times.0.5 mm. The mold containing the interlayer was placed between the upper and lower plates of a hot press and molded at 120 ℃ and an applied pressure of 0 megapascals (MPa) for 10 minutes, resulting in a preheated mold. The mold was held at 120 ℃ at 5MPa for 0.5 min, followed by 120 ℃ at 10MPa for 0.5 min. The mold was vented 8 times, and then kept at 180 ℃ under 10MPa pressure for about 13 minutes to give additional curing, resulting in a crosslinked polyethylene product. The mold was cooled from 180 ℃ to 25 ℃ under 10MPa in 10 minutes and the crosslinked polyethylene product in the form of a compression molded plate was removed. The dissipation factor was tested according to the following method.

The preparation method of the compression molding plate comprises the following steps: a sample of the starting material (e.g., (a) a non-polar polyolefin polymer (e.g., a non-polar ethylene-or propylene-based polymer) or a semiconductor composite) is placed in a mold and pressed in a Grenerd hydraulic press as follows: preheating a press to 150 ℃; subsequently pressureless heating the sample in a mould for 3 minutes to obtain a heated sample; the heated samples were pressed at a pressure of 0.689 megapascals (MPa, 100 pounds per square inch (psi)) for 3 minutes, and then at a pressure of 17.2MPa (2500psi) for 3 minutes; the mold was quenched and held at a pressure of 0.689MPa at 40 ℃ for 3 minutes to give a compression molded plate of the sample.

BET nitrogen surface area test method: BET surface area analysis was performed using a Micromeritics accelerated surface area and porosity instrument (ASAP 2420). The samples were simultaneously evacuated under vacuum at 250 ℃ prior to analysis. The instrument employs a static (volumetric) method of feeding the sample and measures the amount of gas that can be physically adsorbed (physisorbed) on the solid at the temperature of liquid nitrogen. For multi-point BET measurements, the nitrogen absorption volume is measured at a preselected relative pressure point at a constant temperature. The relative pressure is the ratio of the applied nitrogen pressure to the vapor pressure of nitrogen at an analytical temperature of-196 ℃.

Density test method: standard Test Methods for Density and Specific Gravity of Plastics by Displacement (Standard Test Methods for Density and Specific Gravity) method B (for testing liquids other than Water)Solid plastic as in liquid 2-propanol) were measured: results are reported in grams per cubic centimeter (g/cm)³) Is a unit.

Melt index (190 ℃, 2.16 kilograms (kg), "I₂") test method: for nonpolar vinyl polymers, the Standard Test Method for thermoplastic Melt Flow Rate by Extrusion integrator (Standard Test Method for Melt Flow Rates of Thermoplastics) according to ASTM D1238-04, formerly known as "Condition E" and also known as I₂At 190 deg.C/2.16 kg. Results are reported in units of grams dissolved out per 10 minutes (g/10 min.). The nonpolar propylene-based polymer is replicated unless 230 ℃ is used instead of 190 ℃.

Moisture absorption test method: measuring the moisture uptake of the carbon black by drying a carbon black sample overnight in a vacuum oven at 100 ℃, measuring the weight of the dried carbon black sample, placing the dried carbon black sample in a chamber having a well controlled 80% Relative Humidity (RH) and 24 ℃ temperature for 24 hours, obtaining a moisture-containing carbon black sample, weighing the moisture-containing carbon black sample, and calculating the moisture uptake in parts by weight in parts per million using the following equation: moisture uptake (weight of moisture-containing CB sample-weight of dried CB sample) was divided by the weight of dried CB sample.

Oil Absorption Number (OAN) test method: procedure A using ASTM D2414-04, with dibutyl phthalate (DBP).

Phase morphology test method: scanning Electron Microscopy (SEM) was used to characterize the phase morphology of the semiconductor composite. To prepare for analysis, a sample of the compression molded plate prepared by the compression molded plate preparation method was first cut using a razor blade to expose the interior thereof. The exposed interior was polished in a Leica Ultracut EM FC7 cryomicrotome at-80 ℃. Electron micrographs were taken in a FEI Nova NanoSEM 630 electron microscope equipped with a tungsten zirconium field emission electron source operating at 10 kilovolts (kV), an Everhart-Thornley secondary electron detector, and a low voltage high contrast backscattered electron detector.

Rheology test method: viscosity versus angular frequency. Dynamic oscillatory shear rheology was performed with an ARES oscillatory shear rheometer for analysis of viscoelastic behavior. For strain in the linear viscoelastic region, oscillatory shear measurements were performed with a parallel plate geometry (plate diameter 25mm) using a frequency sweep at 0.25% strain for angular frequencies of 0.1 to 100 radians/second (rad/s). The measurement was performed at 160 ℃. Results are reported in pascal-seconds (Pa-s).

Surface energy test method: measurements were made at 23 ℃ from three liquid contact angles using the Owens-Wendt equation. Sample plaques of (a) non-polar polyolefin polymers (e.g., non-polar ethylene-based or propylene-based polymers) were made by compression molding plaque preparation methods (previously described). The surface energy of the sample was calculated based on the liquid contact angle using the OWENS-WENDT method. The contact angle was measured by the sessile drop method (sessile drop) on a KRUSS DSA100 drop shape analyzer (goniometer) using an artificial baseline at a brightness of 100, a contrast of 80 and a frame rate of 50. The three liquids were water, formamide and diiodomethane and were used in a tower-like device with a 0.5 millimeter (mm) stainless steel/polymer needle. The contact angle was fitted using the elliptical (tangent 1) method. For each liquid, at least 6 droplets were analyzed and the average of the results reported. The average values were used to calculate the surface energy by the OWENS-WENDT method.

Thermal cycling test method: the semiconductor composite samples were pressureless heated in a copper mold (placed in a hydraulic press) at 180 ℃ for 3 minutes, followed by heating at a pressure of 0.689MPa (100psi) for 3 minutes and 17.2MPa (2500psi) for 3 minutes. The sample was then quenched to 40 ℃ at a pressure of 0.689MPa (100 psi). This thermal cycle was repeated twice to obtain a thermal cycle sample.

Volume resistivity test method: measurement of Low resistivity Using a Keithley 2700Integr series digital multimeter with a 2-point Probe (1:)<10⁸Ohm-cm (Ω · cm)). Silver paint (conductive silver No. 4817N) was coated to minimize contact resistance between the sample and the electrode, wherein the sample was a compression molded plate prepared by a compression molded plate preparation method with a sample thickness of 1.905mm to 1.203mm (75 mil to 80 mil), a length of 101.6mm, and a width of 50.8 mm. Model 8009 resistivity test chamber using disc sampleCoupled Keithley Model 6517B electrometer measurements have high resistivity (S) ((R))>10⁸Ω cm) prepared as a disc of a compression molded plate sample prepared by a compression molded plate preparation method having a thickness of 1.905mm to 1.203mm (75 mil to 80 mil) and a diameter of 63.5 mm.

Wettability test method: a reverse gas chromatography (IGC) method using an IGC Surface energy analyzer instrument and SEA analysis software, both from Surface Measurement Systems, of alendon, Pennsylvania, USA, was used. The total surface energy of the material (γ (total)) is the sum of the two components, i.e. the dispersed component (γ (dispersed)) and the polar component (γ (polar)): γ (total) ═ γ (polar) + γ (dispersed). The gamma (dispersed) component was measured with the following four alkane gas probes: decane, nonane, octane and heptane, and gamma (dispersion) was measured using the Dorris and Gray method (see below). The gamma (polar) component was measured with two polar gas probes: ethyl acetate and methylene chloride, and gamma (polarity) was analyzed using the Della Volpe scale (D.J. Burnett et al, "AAPS pharmaceutical science technology (AAPS PharmSciTech)," 2010,13, 1511-. Pure carbon black test samples in amounts of about 10 to 20 milligrams (mg) were loaded into separate silanized glass columns (300mm long x 4mm inner diameter). The carbon black packed column was pretreated with helium carrier gas at 100 ℃ and 0% relative humidity for 2 hours to normalize the samples. Measurements were performed with a total helium gas flow rate of 10 standard cubic centimeters per minute (sccm) and methane was used for idle volume correction. The components were measured at 100 ℃ and 0% relative humidity. The surface energy of the carbon black was measured as a function of surface coverage, n/nm, where n is the amount of gas probe adsorbed and nm is the monolayer capacity of the carbon black. The distribution of surface energy as a function of surface coverage reveals the inhomogeneity of the carbon black surface.

Examples of the invention

Vulcan XC 500 furnace carbon black from cabot corporation. BET nitrogen surface area, measured by the BET nitrogen surface area test method, of 65m²(ii)/g; by passingOAN was 148mL/100g as measured by ASTM D2414-04; and the moisture absorption was 10,000ppm as measured by the moisture absorption test method; and the surface wettability profile is characterized by: wettability at 0.02 surface coverage was 0.0115, and wettability at 0.04 surface coverage was 0.0101, and wettability at 0.06 surface coverage was 0.0099, and wettability at 0.08 surface coverage was 0.0111, and wettability at 0.10 surface coverage was 0.0117.

Acetylene black AB 100% -01 carbon black from Soltex. BET nitrogen surface area, measured by the BET nitrogen surface area test method, of 77m²(ii)/g; OAN is 187 to 202mL/100g as measured by ASTM D2414-04; the moisture absorption amount was 3,000ppm as measured by the moisture absorption amount test method; and the surface wettability profile is characterized by: wettability at 0.02 surface coverage was 0.0101, and wettability at 0.04 surface coverage was 0.0108, and wettability at 0.06 surface coverage was 0.0111, and wettability at 0.08 surface coverage was 0.0112, and wettability at 0.10 surface coverage was 0.0113.

Component (a 1): the nonpolar polymer (A) as the nonpolar vinyl polymer is a polymer having a density of 0.918 g/cc (g/cm)³) And melt index (I)₂) (ASTM D1238-04, 190 ℃, 2.16kg) 8.0 grams/10 minutes (g/10min.) of Low Density Polyethylene (LDPE). With product DOW^TMLDPE722 is available from the Dow chemical company of Midland, Michigan, USA, Michigan.

Component (a 2): (A) a non-polar polyolefin polymer which is a non-polar vinyl polymer, said non-polar vinyl polymer having a density of 0.905g/cm³And melt index (I)₂) (ASTM D1238-04, 190 ℃, 2.16kg) 0.9 g/10min of Linear Low Density Polyethylene (LLDPE). Obtained as product DFNA-1477NT from the Dow chemical company.

Component (a 3): (A) a non-polar polyolefin polymer which is a non-polar vinyl polymer, said non-polar vinyl polymer being produced by UNIPOL^TMHaving a monomodal molecular weight distribution and a density of 0.920g/cm, prepared by a gas-phase polymerization process³And isMelt index (I)₂) (ASTM D1238-04, 190 ℃, 2.16kg) 0.55 g/10min of Linear Low Density Polyethylene (LLDPE). Obtained as product DFNA-2065 from the Dow chemical company.

Component (B1): (B) ULW-CB, a LITX 50 conductive additive from Cabot corporation. BET nitrogen surface area of 56m, as measured by the BET nitrogen surface area test method²(ii)/g; OAN of 125 to 145mL/100g as measured by ASTM D2414-04; the moisture absorption was 520ppm as measured by the moisture absorption test method; and the surface wettability profile is characterized by: the wettability at 0.02 surface coverage was 0.0014, and the wettability at 0.04 surface coverage was 0.0039, and the wettability at 0.06 surface coverage was 0.0051, and the wettability at 0.08 surface coverage was 0.0061, and the wettability at 0.10 surface coverage was 0.0069.

Ingredient (D1): (D) an antioxidant which is a1, 2-dihydro-2, 2, 4-trimethylquinoline homopolymer, also known as poly (1, 2-dihydro-2, 2, 4-trimethylquinoline).

Ingredient (C1)/(D1)/(I1): a processing aid-containing masterbatch formulation comprising 74.9 wt% (C1) DFDA-7047LLDPE, 25.0 wt% (I1) Viton FreeFlow 23 processing aid and 0.1 wt% (D1) tetrakis (methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate)) methane (antioxidant). Plastomer (C1) DFDA-7047LLDPE as a density of 0.918g/cm³And a melt index I2 of 1.0 g/10min linear low density polyethylene and obtained from the dow chemical company. Viton FreeFlow 23 is a fluoroelastomer processing aid available from kemu corporation.

Comparative examples 1 to 3(CE1 to CE 3): comparative composites prepared using ingredients (a1) DOW LDPE722 and Vulcan XC 500 furnace carbon black. The semiconductor materials of CE1 to CE3 were obtained by melt-mixing the component (A1) and Vulcan XC 500 according to the semiconductor composite preparation method. The CE1 to CE3 samples were pressed separately to form plates according to the compression molding plate preparation method.

Comparative examples 4 to 6(CE4 to CE 6): comparative composites were prepared using the composition (A1) DOW LDPE722 and acetylene black AB 100% -01 carbon black. Semiconductor materials of CE4 to CE6 were obtained by melt-mixing the ingredients (a1) and acetylene black AB 100% -01 according to the semiconductor composite preparation method. The CE4 to CE6 samples were pressed separately to form plates according to the compression molding plate preparation method.

Inventive examples 1-5 (IE 1-IE 5): the inventive semiconductive composite was prepared using ingredient (A1) DOW LDPE722 and ingredient (B1) LITX 50 carbon black. Semiconductor materials of IE1 to IE5 were obtained by melt-mixing the components (a1) and (B1) according to the semiconductor composite preparation method. Samples IE1 through IE5 were pressed separately according to the compression molded panel preparation method to form panels.

Inventive examples 6 and 7(IE6 and IE 7): the inventive semiconductive composite was prepared using ingredient (A1) DOW LDPE722, ingredient (A2) Univation DFNA-2065 and ingredient (B1) LITX 50 carbon black. Semiconductor materials of IE6 and IE7 were obtained by melt mixing the ingredients (a1), (a2), (B1) and (C1) according to the semiconductor composite preparation method, except using an internal c.w. brabender premixer for 10 minutes at 180 ℃ at a motor speed of 40 rpm. Samples of IE6 and IE7 were pressed separately at 150 ℃ according to the compression molded panel preparation method to form panels having a thickness of 1.27mm (50 mils).

Table 1: composite materials CE1 through CE6 were compared to the test results. ("0" means 0.00, N/m means not measured)

As shown by the data in table 1, CE1 through CE6 have high electrical resistivity at a given range of total BET N2 surface area of carbon black in the composite desired for the non-semiconducting layer: at 20.0 to 30.0m²The total BET N2 surface area Log (volume resistivity) value of the carbon black in the composite is>0.7Log (Ohm-cm); at 15.0 to 20.0m²The total BET N2 surface area of the carbon black in the composite is>2Log (Ohm-cm); at 10.0 to 15.0m²The total BET N2 surface area of the carbon black in the composite is>4Log (Ohm-cm); at 7.5 to 10m²The total BET N2 surface area of the carbon black in the composite is>10Log (Ohm-cm); at 5 to 7.5m²Total BET N2 of carbon Black in composite/gAt a surface area of>16Log (Ohm-cm); at 2.5 to 5.0m²The total BET N2 surface area of the carbon black in the composite is>17.1Log (Ohm-cm). Comparative materials CE1 through CE6 contained previously conductive carbon blacks at various loadings to show the loading-conductivity relationship. The results show that volume resistivities of less than 100,000Ohm-cm require more than 20 weight percent loading of these prior carbon blacks. This high loading makes melt processing and extrusion/stranding comparative formulations difficult and results in undesirable amounts of moisture pick-up during operable use of power cables containing the same.

Table 2: semiconductor composites IE1 to IE7 and test results. ("0" means 0.00, N/m means not measured)

As shown by the data in table 2, IE1 through IE7 have low resistivity at a given range of total BET N2 surface area of carbon black in the composite that is highly desirable for the semiconducting layer: at 20.0 to 30.0m²(ii) the total BET N2 surface area of the carbon black in the composite has a Log (volume resistivity) value of 0.7Log (Ohm-cm) or less; at 15.0 to 20.0m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 2Log (Ohm-cm); at 10.0 to 15.0m²(ii) a total BET N2 surface area of ≦ 4Log (Ohm-cm) for carbon black in the composite; at 7.5 to 10m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 10Log (Ohm-cm); at 5.0 to 7.5m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 16Log (Ohm-cm); and is in the range of 2.5 to 5.0m²The carbon black in the composite has a total BET N2 surface area of ≦ 17.1Log (Ohm-cm). Inventive examples IE1 through IE7 clearly show that greater conductivity (lower volume resistivity) can be achieved at the same ULW-CB loading as the carbon black loading used in the comparative examples. Volume resistivities of less than 100,000Ohm-cm (less than 5Log (Ohm-cm)) are achieved at ULW-CB loadings of less than 20 wt%. This provides an improved balance of conductivity and carbon black loading.

Claims (15)

1. A semiconductor composite consisting essentially of: (A) a non-polar polyolefin polymer; and a conductively effective amount of (B) ultra-low wettability carbon black (ULW-CB) having a BET nitrogen surface area of 35 to 190 square meters per gram (m) as measured by the Brunauer-Emmett-Teller (BET) nitrogen surface area test method (described later)²(iv)/g); and an Oil Absorption Number (OAN) of 115 to 180 milliliters of oil per 100 grams (mL/100g) as measured by the oil absorption number test method.

2. The semiconductor composite of claim 1, wherein the (B) ULW-CB is characterized by any one of the limits (i) to (iii): (i) the BET nitrogen surface area of the (B) ULW-CB is 40 to 63m as measured by the BET nitrogen surface area test method²(ii)/g; and an OAN of 120 to 150mL/100g as measured by the oil absorption number test method; (ii) the BET nitrogen surface area of the (B) ULW-CB is 120 to 180m as measured by the BET nitrogen surface area test method²(ii)/g; and an OAN of 150 to 175mL/100g as measured by the oil absorption number test method; and (iii) said (B) ULW-CB is a ULW-CB blend having (i) and (ii).

3. A semiconductor composite consisting essentially of: (A) a non-polar polyolefin polymer; and a conductively effective amount of (B) an ultra-low wettability carbon black (ULW-CB) having a surface wettability profile characterized by: the wettability at 0.02 surface coverage is 0.0101 or less, and the wettability at 0.04 surface coverage is 0.0101 or less, and the wettability at 0.06 surface coverage is 0.0099 or less, and the wettability at 0.08 surface coverage is 0.0111 or less, and the wettability at 0.10 surface coverage is 0.0113 or less, as measured by reverse gas chromatography (IGC) according to the wettability test method.

4. The semiconductor composite of any one of claims 1 to 3, wherein the (B) ULW-CB is characterized by any one of the limitations (i) to (vii): (i) a BET nitrogen surface area of 40 to 180m as measured by the BET nitrogen surface area test method²/g；(ii) A water absorption of 400 to 2400 parts per million (ppm, weight) as measured by the moisture absorption test method; (iii) surface wettability profiles characterized by: a wettability at 0.02 surface coverage of ≦ 0.0058, and a wettability at 0.04 surface coverage of ≦ 0.0070, and a wettability at 0.06 surface coverage of ≦ 0.0075, and a wettability at 0.08 surface coverage of ≦ 0.0086, and a wettability at 0.10 surface coverage of ≦ 0.0091, measured by IGC according to the wettability test method; (iv) both (i) and (ii); (v) (ii) both (i) and (iii); (vi) both (ii) and (iii); (vii) (iv) a combination of (i), (ii), and (iii).

5. The semiconducting composite of any of claims 1-4, free of any carbon black other than the ultra-low wettability carbon black.

6. The semiconductor composite according to any one of claims 1 to 5, characterized in that any one of (i) to (v): (i) consisting essentially of: 61.0 to 99.0 wt% of the (A) non-polar polyolefin polymer; and 39.0 wt% to 1.0 wt% of said (B) ULW-CB; the above being the total weight of the semiconductor material; (ii) the non-polar polyolefin polymer (A) is a non-polar vinyl polymer; (iii) both (i) and (ii); (iv) the non-polar polyolefin polymer (A) is a non-polar propylene-based polymer; and (v) both (i) and (iv).

7. The semiconducting composite of any of claims 1 through 6, further consisting essentially of at least one additive selected from the group consisting of: (C) a plastomer; (D) an antioxidant; (E) an organic peroxide; (F) a scorch retarder; (G) an alkenyl functional coagent; (H) a nucleating agent; (I) a processing aid; (J) an extender oil; (K) stabilizers (e.g., compounds that inhibit Ultraviolet (UV) light-related degradation).

8. The semiconductor composite of any one of claims 1 to 7, characterized by a first series of embodiments thereof having different amounts of the (B) ULW-CB, wherein the first series has a log (volume resistivity) profile of <1.0log (Ohm-cm) at 33 wt% electrically conductive effective amount and <4.5log (Ohm-cm) at 20 wt% electrically conductive effective amount and <10.0log (Ohm-cm) at 15 wt% electrically conductive effective amount and <16.5log (Ohm-cm) at 10 wt% electrically conductive effective amount and <17.5log (Ohm-cm) at 5 wt% electrically conductive effective amount, as measured by volume resistivity test method, wherein the electrically conductive effective amount of the (B) ULW-CB is based on the total weight of the semiconductor composite.

9. Semiconductor composite according to any of claims 1 to 8, characterized in that a second series of its embodiments of the (B) ULW-CB, having a different total BET N2 surface area, has a log (volume resistivity) profile of 15.0 to 20.0m, measured by the volume resistivity test method²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 2Log (Ohm-cm); and is between 10.0 and 15.0m²(ii) a total BET N2 surface area of ≦ 4Log (Ohm-cm) for carbon black in the composite; and is in the range of 7.5 to 10m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 10Log (Ohm-cm); and is between 5.0 and 7.5m²(ii) the total BET N2 surface area of the carbon black in the composite is ≦ 16Log (Ohm-cm); and is in the range of 2.5 to 5.0m²The carbon black in the composite has a total BET N2 surface area of ≦ 17.1Log (Ohm-cm).

10. A method of making the semiconductive composite according to any of claims 1 to 9, comprising mixing the (B) ultra-low wettability carbon black (ULW-CB) into the melt of the (a) non-polar polyolefin polymer, resulting in the semiconductive composite as a molten blend comprising ingredients (a) and (B).

11. A crosslinked polyethylene product which is the product of curing the semiconducting composite of any of claims 1 to 9.

12. An article comprising a semiconductive composite according to any of claims 1 to 9 or made by the process according to claim 10, or a crosslinked polyethylene product according to claim 11, in shaped form.

13. An electrical conductor device comprising a conductive core and a semiconducting layer at least partially covering the conductive core, wherein at least a portion of the semiconducting layer comprises the semiconducting composite of any of claims 1-9, the semiconducting composite made by the process of claim 10, or the crosslinked polyethylene product of claim 11.

14. A method of conducting electricity, the method comprising applying a voltage across a conductive core of an electrical conductor device according to claim 13 so as to generate a current through the conductive core.

15. A thermally cycled semiconductor composite made by subjecting the semiconductor composite of any one of claims 1 to 9 to thermal cycling comprising heating the semiconductor composite to 170 ℃ to 190 ℃ for 1 to 5 minutes and subsequently cooling to 30 ℃ resulting in a cooled thermally cycled semiconductor composite.